WO2019172156A1 - Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit - Google Patents

Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit Download PDF

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Publication number
WO2019172156A1
WO2019172156A1 PCT/JP2019/008277 JP2019008277W WO2019172156A1 WO 2019172156 A1 WO2019172156 A1 WO 2019172156A1 JP 2019008277 W JP2019008277 W JP 2019008277W WO 2019172156 A1 WO2019172156 A1 WO 2019172156A1
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imprints
group
composition
ring
formula
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PCT/JP2019/008277
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English (en)
Japanese (ja)
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直也 下重
雄一郎 後藤
旺弘 袴田
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富士フイルム株式会社
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Priority to JP2020505001A priority Critical patent/JP7017623B2/ja
Publication of WO2019172156A1 publication Critical patent/WO2019172156A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to the provision of an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit.
  • the imprint method is to transfer a fine pattern by pressing a mold against a curable composition, curing the composition, and then peeling the mold. Attempts have been made to apply this method to the field of precision processing such as the manufacture of semiconductor integrated circuits.
  • the imprint method eliminates the need for expensive fine processing devices such as steppers and electron beams. Since the manufacturing cost is reduced, the process is simple, and high resolution and high throughput can be realized, research for mass production of devices is being actively conducted in various fields.
  • the imprint method there is a technique in which a photosensitive resin composition is used as a material applied for patterning and processing is performed by combining a light-transmitting mold.
  • a pattern is formed on the cured film of the photosensitive resin composition disposed on the substrate by irradiating light through a mold, and this is used as an insulating member or as a mask for further processing.
  • What uses ultraviolet (UV) as light to irradiate may be called especially the UV nanoimprint method.
  • the optical nanoimprinting method including the UV nanoimprinting method processing at room temperature is possible, unlike the thermal nanoimprinting method that requires heating using a thermosetting resin composition. Therefore, it can be widely applied as a technique for realizing high quality in the manufacture of semiconductor devices and the like that dissipate heat.
  • Patent Document 1 contains a resin having at least one group selected from a (meth) acryloyloxy group, an alkoxycarbonyl group, an oxiranyl group, and an oxetanyl group, a nonionic surfactant, and a solvent.
  • a resin composition for forming an underlayer film is disclosed. Accordingly, it is described that the variation in the residual film thickness after pressing the mold is small, and the variation in the line width distribution of the pattern after pressing is less likely to occur.
  • the formation of a fine pattern by imprinting is extremely efficient as compared with the technique by photolithography, and the manufacturing cost and productivity for manufacturing a semiconductor device can be greatly improved.
  • semiconductor technology advances further improvements in pattern miniaturization and manufacturing quality are required.
  • the lower film forming composition for imprinting in order to increase the adhesion between the substrate and the curable composition for imprinting, the lower film forming composition for imprinting is used, and the coating film of the lower film forming composition for imprinting is used.
  • it has been studied to apply a curable composition for imprints to a surface to form a film there is a demand for further improvement of the wettability of the film.
  • the present invention is superior in the wettability of the curable composition for imprints to the coating film of the underlayer film forming composition for imprints, and the adhesion between the underlayer film and the imprint layer formed from these compositions. It is an object of the present invention to provide an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit using these.
  • the above problems can be solved by employing a polymer capable of generating a specific desorption component in the composition for forming an underlayer film for imprinting. It was. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 27>.
  • An underprint film-forming composition for imprints comprising a polymer and a solvent, wherein when the above-mentioned undercoat film-forming composition for imprints is formed into a film and baked at 80 ° C., from the polymer, the following formula (r1) Or a composition for forming an underlayer film for imprinting, wherein a compound represented by (r2) and having a molecular weight of 210 or more is eliminated;
  • R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
  • composition for forming an underlayer film for imprints according to ⁇ 1>, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1);
  • R r1 and R r2 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent.
  • composition for forming an underlayer film for imprints according to ⁇ 1> or ⁇ 2>, wherein the polymer includes a group represented by any of the following formulas (R-1) to (R-4);
  • R 1 to R 3 are each independently a monovalent substituent
  • R 4 to R 12 are each independently a hydrogen atom or a monovalent substituent
  • X is a bonding position to the main chain of the polymer. Represents.
  • ⁇ 4> From the polymer containing a substituent represented by any one of the above formulas (R-1) to (R-4), the C—O bond in the formula is decomposed, and the above formula (r1) or (r2) The composition for forming an underlayer film for imprints according to ⁇ 3>, wherein a compound having a molecular weight of 210 or more is eliminated.
  • ⁇ 5> The composition for forming an underlayer film for imprints according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer contains a polymerizable group.
  • ⁇ 6> The underlayer film-forming composition for imprints according to ⁇ 5>, wherein the polymerizable group includes a (meth) acryloyl group.
  • ⁇ 7> The composition for forming a lower layer film for imprints according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer includes an aromatic ring.
  • ⁇ 8> The imprint according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer includes at least one structural unit represented by any of the following formulas (1) to (6): An underlayer film forming composition;
  • R P4 represents a hydrogen atom or a methyl group;
  • R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2).
  • ⁇ 9> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 8>, wherein the compound represented by the formula (r1) or (r2) includes an aromatic ring.
  • ⁇ 13> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 12>, wherein the compound represented by the formula (r1) or (r2) has a molecular weight of 1000 or less.
  • ⁇ 14> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 13>, further comprising an elimination reaction accelerator or a precursor thereof.
  • ⁇ 15> The composition for forming an underlayer film for imprints according to any one of ⁇ 1> to ⁇ 14>, further comprising a photopolymerization initiator.
  • ⁇ 16> Formation of an underprint film for imprinting according to any one of ⁇ 1> to ⁇ 15>, wherein the compound represented by the formula (r1) or (r2) has a surface tension of 35 to 55 mN / m Composition.
  • ⁇ 19> A kit comprising the imprint underlayer film forming composition according to any one of ⁇ 1> to ⁇ 17>, and an imprint curable composition comprising a polymerizable compound.
  • a ⁇ HSP value calculated by the following formula (H1) is 5
  • the kit according to ⁇ 19>, which is: ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1) ⁇ D is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2), ⁇ P is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hans
  • ⁇ 21> A lower layer film formed from the lower layer film forming composition according to any one of ⁇ 1> to ⁇ 17>.
  • ⁇ 22> A laminate formed from the kit according to ⁇ 19> or ⁇ 20>, The laminated body which has the lower layer film formed from the said lower layer film formation composition for imprints, and the imprint layer formed from the said curable composition for imprints, and located in the surface of the said lower layer film.
  • ⁇ 23> A method for producing a laminate using the kit according to ⁇ 19> or ⁇ 20>, wherein the surface of the lower layer film formed from the lower layer film forming composition for imprinting is cured for imprinting.
  • the manufacturing method of a laminated body including applying an adhesive composition.
  • the method further includes the step of applying the lower layer film-forming composition for imprinting on the substrate in a layered manner, and heating the lower layer film forming composition for imprinting applied to the layered state at 80 to 250 ° C.
  • ⁇ 26> A method for producing a cured product pattern using the kit according to ⁇ 19> or ⁇ 20>, wherein a lower layer film is formed on a substrate by applying the lower film forming composition for imprinting Contact the film forming step, the application step of applying the curable composition for imprints to the surface of the lower layer film, the curable composition for imprints, and the mold having a pattern for transferring the pattern shape.
  • Production method. ⁇ 27> A method for producing a circuit board, comprising a step of obtaining a cured product pattern by the production method according to ⁇ 26>.
  • the wettability of the curable composition for imprints with respect to the coating film of the lower layer film-forming composition for imprints, and the adhesion between the lower layer film and the imprint layer formed from these compositions are improved. Became possible.
  • imprint preferably refers to pattern transfer having a size of 1 nm to 10 mm, more preferably pattern transfer (nanoimprint) having a size of approximately 10 nm to 100 ⁇ m.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • light includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation.
  • radiation include microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays.
  • Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used.
  • the light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
  • the temperature in the present invention is 23 ° C. unless otherwise specified.
  • the underlayer film-forming composition for imprints of the present invention contains a polymer and a solvent.
  • the following formula (r1) or (r2) is determined from the polymer. Is desorbed (hereinafter also referred to as a desorbing component).
  • the generation of a low molecular component causes a decrease in interfacial tension on the surface of the lower layer film, and accordingly, wettability is improved.
  • the curable component of the curable composition for imprints penetrates into the region where the low molecular component was present in the lower layer film, and the portion is cured, thereby lower layer film It is considered that the adhesion between the cured product and the cured product is improved.
  • ⁇ Underlayer film-forming composition for imprint> when the composition for forming a lower layer film for imprinting is formed into a film and baked at 80 ° C., a compound represented by the following formula (r1) or (r2) and having a molecular weight of 210 or more is desorbed from the polymer. To do.
  • the above compound is referred to as a desorbing component.
  • the desorbing component is a component that desorbs from the polymer when the underlayer film forming composition for imprinting is formed into a film and baked at 80 ° C., and is a compound having a predetermined structure and having a molecular weight of 210 or more. is there.
  • the desorption component in the first embodiment of the present invention is represented by the following formula (r1) or (r2).
  • the desorbing component is a compound represented by the formula (r1) or (r2)
  • the polymerization initiator in the curable composition for imprinting diffuses into the underlayer film forming composition for imprinting, and for imprinting.
  • the composition for forming a lower layer film for imprints is cured, and the adhesion between the curable composition for imprints and the lower layer film is more excellent.
  • R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
  • the compound represented by the formula (r1) or (r2) is preferably represented by the following formula (r1-1).
  • R r1 and R r2 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent.
  • the leaving component (the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1)) preferably contains an aromatic ring (preferably the following ring aCy or hCy).
  • an aromatic ring preferably the following ring aCy or hCy.
  • at least one of R r1 and R r2 of formula (r1), at least one of R r4 to R r6 of formula (r2), and at least one of R r1 and R r2 of formula (r1-1) are aromatic rings It is preferable to contain.
  • the aromatic ring is preferably the following ring aCy or hCy.
  • aromatic ring is an aromatic ring
  • aromatic ring examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenyl ring, terphenyl ring, indene ring, indane ring, triphenylene Ring, tetraphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring and the like.
  • the aromatic ring may have a structure in which a plurality of aromatic rings are connected with or without a connecting group L, and examples thereof include a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring.
  • examples of the structure in which a plurality of benzene rings are linked include those represented by the following formulas Ar1 to Ar5.
  • a straight line drawn outward from the center of the benzene ring indicates a bond. It is bonded to an arbitrary linking group through this single bond, or is bonded to L 1 , L 2 , P of the following formula (T1), or the main chain of the polymer through or without it. Means that.
  • a 1 is a divalent linking group, and examples of the linking group L are preferable.
  • An alkylene group which may be substituted with a fluorine atom (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms being preferred) Further preferred are a carbonyl group, an oxygen atom, a sulfonyl group, a sulfinyl group, and —NR N —.
  • a 2 represents a nitrogen atom, a trivalent linking group containing a phosphorus atom, or a methine group.
  • the carbon number thereof is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 5.
  • Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, isoindole.
  • the aromatic heterocyclic ring may have a structure in which a plurality of ring structures are connected through or without the connecting group L.
  • the aromatic heterocycle shown here is referred to as ring hCy.
  • the aromatic ring contained in the leaving component is preferably a benzene ring.
  • the aromatic ring may have a substituent T as long as the effects of the present invention are achieved.
  • substituents T they may be bonded to each other, or may be bonded to a ring in the formula through or without a linking group L to form a ring.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the leaving component preferably contains a polymerizable group.
  • the polymerizable group include groups containing an ethylenically unsaturated group, an epoxy group, a glycidyl group, an oxetane group, and the like.
  • the ethylenically unsaturated group include a group including a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.
  • the polymerizable group exemplified here is referred to as a polymerizable group Ps.
  • the polymerizable group Ps preferably contains a (meth) acryloyl group or a (meth) acryloyloxy group.
  • at least one of R r1 and R r2 in formula (r1), at least one of R r4 to R r6 in formula (r2), and at least one of R r1 and R r2 in formula (r1-1) are polymerizable.
  • it contains a group.
  • the polymerizable group the polymerizable group Ps is preferable.
  • the elimination component preferably contains an ethylenic double bond. In particular, it is preferable that an ethylenic double bond is formed by elimination from the polymer. By such desorption, the effect of adhesion is exhibited.
  • R r1 , R r2 , R r4 , R r5 , R r6 is a substituent
  • examples of the substituent T described below are examples of the substituent.
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
  • an arylalkyl group preferably 7 to 23 carbon atoms, 7 To 19 are more preferable, and 7 to 11 are more preferable
  • a group represented by the following formula (RL-1) is preferable.
  • at least R r2 or R r6 is a group represented by the following formula (RL-1).
  • L R1 and L R2 are each independently a single bond or a linking group
  • Ar R is a linking group containing an aromatic ring
  • P R is a group having a polymerizable group.
  • nr is an integer of 0 to 8
  • mr is an integer of 1 to 4.
  • L R1 is, 1 + mr -valent aromatic ring (examples of the aCy or hCy is preferred), alicyclic (e.g. below alicyclic fCy is preferred), a linear or branched radical of an alkane structure (having 1 to 40 carbon atoms are preferred 1 to 30 is more preferable, and 1 to 20 is more preferable), a linear or branched alkene structure group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and further preferably 2 to 20 carbon atoms), or A group having a linear or branched alkyne structure (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, still more preferably 2 to 20 carbon atoms) is preferable.
  • alicyclic e.g. below alicyclic fCy is preferred
  • a linear or branched radical of an alkane structure having 1 to 40 carbon atoms are preferred 1 to 30 is more preferable,
  • Examples of the linking group of L R2 are preferably the following linking group L or a linking group Lh containing the following hetero atom.
  • an alkylene group preferably having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms
  • an arylene group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 10 carbon atoms. Is more preferable
  • (oligo) alkyleneoxy group the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3; the number of repetitions is 1 to 50).
  • L R2 may be bonded to L R1 via a linking group L or not to form a ring.
  • Ar R is a linking group containing an aromatic ring. However, when nr is 0, Ar R is a substituent containing an aromatic ring.
  • the aromatic ring is preferably the above ring aCy or hCy.
  • examples of the linking group include the following linking groups L.
  • an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) 6 is more preferable), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3; 1 to 50, preferably 1 to 40, more preferably 1 to 30), and an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).
  • Ar R is not through or via a linking group L, L R1, L R2 or may be bonded to
  • P R is the volatilization having a polymerizable group, the polymerizable group, examples of the polymerizable group Ps are preferred.
  • P R is not through or via a linking group L, they may form a ring with L R1, L R2.
  • L R1, L R2, Ar R , P R may have a substituent T to the extent that the effects of the present invention.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • Nr is an integer of 0 to 8, preferably 0 to 6, more preferably 0 to 4, and still more preferably 0 to 2.
  • mr is an integer of 1 to 4, preferably 1 or 2.
  • R r3 examples include CH 2 (second embodiment described below), CHR r8 , and C (R r9 ) 2 .
  • R r8 and R r9 are each independently a substituent T described later, and among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), alkenyl group Groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 3 carbon atoms)
  • An aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms
  • an arylalkyl group preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and 7
  • the linking group Lh containing a hetero atom includes an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, —NR N —, an (oligo) alkyleneoxy group (of the alkylene group in one constituent unit).
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), or these Examples of the linking group include a combination.
  • the number of atoms constituting the linking group Lh containing a hetero atom is preferably from 1 to 100, more preferably from 1 to 70, particularly preferably from 1 to 50, excluding hydrogen atoms.
  • the number of linking atoms of Lh is preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 15, and still more preferably 1 to 10.
  • the (oligo) alkyleneoxy group means an alkyleneoxy group or an oligoalkyleneoxy group.
  • the (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
  • the linking group is a group capable of forming a salt such as when —NR N — or a carboxyl group is substituted, the group may form a salt.
  • substituent T examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 are more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms are preferable and 2 to 6 carbon atoms are preferable).
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms
  • an arylalkyl group preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms. 7 to 11 are more preferable
  • an alkenyl group preferably 2 to 24 carbon atoms, more preferably 2
  • hydroxyl group preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6
  • thiol group carboxyl group, aryl group (carbon A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an alkoxyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, To 3 are more preferable)
  • an aryloxy group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms
  • an acyl group preferably having 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms).
  • acyloxy groups preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms
  • aryloyl groups preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms. More preferably, 7 to 11 are more preferable
  • aryloyloxy group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • carbamoyl group preferably 1 to 12 carbon atoms are preferable).
  • a sulfamoyl group (having 0 to 12 carbon atoms is preferable, 0 to 6 is more preferable, and 0 to 3 is more preferable).
  • a sulfo group, an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms).
  • a heterocyclic group preferably having a carbon number of 1 to 12, preferably 1 to 8, more preferably 2 to 5, and preferably including a 5-membered or 6-membered ring
  • RN represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 are more preferable), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms).
  • an arylalkyl group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • a hydrogen atom preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • the alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched.
  • the substituent T may further have a substituent T.
  • the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.
  • the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.
  • an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an (oligo) alkyleneoxy group (of the alkylene group in one structural unit)
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and the arylene group ( Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thi
  • the alkylene group may have the substituent T.
  • the alkylene group may have a hydroxyl group.
  • the number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms.
  • the number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, in the case of —CH 2 — (C ⁇ O) —O—, there are 6 atoms involved in the connection, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atom involved in the connection is —C—C—O—, which is three.
  • the number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6.
  • the alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
  • the linking group is a group capable of forming a salt such as —NR N —, the group may form a salt.
  • the desorption component has a molecular weight of 210 or more.
  • the molecular weight of the desorbing component is preferably 210 or more, more preferably 250 or more, and even more preferably 300 or more.
  • the upper limit is practically 1000 or less.
  • the surface tension of the desorbing component is preferably 28 mN / m or more, more preferably 30 mN / m or more, further preferably 36 mN / m or more, and still more preferably 38 mN / m or more. 40 mN / m or more is even more preferable, and 42 mN / m or more is even more preferable.
  • the upper limit is preferably 80 mN / m or less, more preferably 60 mN / m or less, and still more preferably 50 mN / m or less.
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 19.5. Even more preferred;
  • the polar term component (p component) is preferably from 2.0 to 9.0, more preferably from 3.0 to 6.0, and preferably from 3.5 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 3.0 to 12.0, more preferably 4.7 to 7.0, and more preferably 5.0 to 6.5. Is more preferable.
  • the polymer used in the present invention (hereinafter, this polymer may be referred to as a specific polymer) is obtained when the underlayer film forming composition for imprinting containing this specific polymer is formed into a film and baked at 80 to 250 ° C.
  • a wide variety of polymers can be used that desorb the desorbing component from the polymer. More specifically, the specific polymer is preferably a polymer having a group serving as a leaving component in the side chain. In the present invention, preferably 30% by mass or more, more preferably 40% by mass or more of all structural units constituting the polymer are structural units capable of desorbing a desorbing component. The upper limit is not particularly defined, and may be 100% by mass.
  • the desorbing component is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more of the mass of the specific polymer.
  • the upper limit is not particularly defined, but is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
  • the specific polymer preferably contains a substituent represented by any of the following formulas (R-1) to (R-4).
  • R 1 to R 3 are each independently a monovalent substituent
  • R 4 to R 12 are each independently a hydrogen atom or a monovalent substituent
  • X is a bonding position to the main chain of the polymer. Represents.
  • R 4 to R 6 , R 7 to R 9 , and R 10 to R 12 are not all hydrogen atoms.
  • a group containing a carbon atom bonded to an oxygen atom in formula (R-1), that is, a carbon atom substituted by R 1 to R 3 (hereinafter, the carbon atom at this position is referred to as an ⁇ carbon atom in each formula) is a second group.
  • a primary alkyl group or a tertiary alkyl group is preferred.
  • the group containing an ⁇ carbon atom is preferably a secondary alkyl group or a tertiary alkyl group.
  • the group containing the ⁇ carbon atom in the formulas (R-3) and (R-4) is preferably a primary alkyl group or a secondary alkyl group.
  • At least one of R 1 to R 3 is preferably a substituent, and at least two are preferably substituents.
  • At least one of R 4 to R 6 is preferably a substituent, and at least two are preferably substituents.
  • At least one of R 7 to R 9 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent.
  • At least one of R 10 to R 12 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent.
  • R 1 to R 3 , R 4 to R 6 , R 7 to R 9 , and R 10 to R 12 may be bonded to each other to form a ring.
  • R 1 to R 12 may further have a substituent T as long as the effects of the present invention are exhibited.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the C—O bond in the formula is decomposed from the polymer containing a substituent represented by any one of the formulas (R-1) to (R-4), and the formula (r1) or (r2)
  • a compound represented by the formula (r1-1) and having a molecular weight of 210 or more is preferably eliminated.
  • the carbon atom substituted by R r1 and R r2 in formula (r1) (the carbon atom in the second position with the carbon atom contained in R r3 as the first position) is removed from the R in formula (R-1) before the elimination.
  • 1 to R 3 is preferably a carbon atom ( ⁇ carbon atom) to be substituted.
  • the carbon atom at the 2-position of the formula (r1) is preferably a carbon atom substituted by R 4 to R 6 of the formula (R-2) before elimination.
  • the tertiary carbon atom substituted by R r4 to R r6 is a carbon atom substituted by each of the ⁇ carbon atoms, that is, R 1 to R 3 in the formula (R-1) before elimination.
  • An atom or R 4 to R 6 in formula (R-2) is preferably a carbon atom to be substituted.
  • R 1 to R 3 is decomposed at the position of C—O, and a double bond is formed at the elimination position (alpha carbon atom position) on the elimination component side.
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms
  • more preferably an ethyl group more preferably an ethyl group, and further preferably a methyl group.
  • R 4 to R 6 is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), It is more preferably an ethyl group, and further preferably a methyl group.
  • the specific polymer also preferably contains a polymerizable group, the polymerizable group is preferably a polymerizable group Ps, and more preferably contains a (meth) acryloyl group.
  • the polymerizable group may have a constituent unit having a group capable of leaving the leaving component, or may have another constituent unit. In the present invention, it is preferable that at least a constituent unit other than the constituent unit having a group capable of leaving the leaving component has a polymerizable group.
  • the proportion of the structural unit having a polymerizable group is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, and more preferably 80 to 100 mol% of the total structural units. More preferably.
  • the specific polymer preferably includes an aromatic ring, and the aromatic ring is preferably a ring aCy or hCy.
  • the aromatic ring may be contained in a constituent unit having a group capable of leaving the leaving component, or may be contained in another constituent unit. In the present invention, it is preferable that at least the structural unit having a group capable of leaving the leaving component has an aromatic ring.
  • the proportion of the structural unit containing an aromatic ring is preferably 10 to 100 mol%, and more preferably 40 to 100 mol% of the total structural units.
  • the type of the specific polymer is not particularly limited.
  • the specific polymer further preferably includes at least one structural unit represented by any of the following formulas (1) to (6).
  • R P4 is a hydrogen atom or a methyl group.
  • R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1), and is preferably a group represented by the formula (R-1) to (R -4).
  • a linking group may be interposed between X in the formulas (R-1) to (R-4) and the main chain atom. Examples of the linking group include the linking group L. In this case, the linking group may be trivalent or more. In that case, the structural unit of the polymer has a plurality of groups represented by the formulas (R-1) to (R-4) through the linking group.
  • Examples of the trivalent or higher linking group include a group having an aromatic ring (aCy, hCy) structure, a group having an alkane structure (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms), A group having 2 to 40 carbon atoms (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), and an alkyne structure group (2 to 40 carbon atoms are preferable, 2 to 30 carbon atoms are more preferable, and 2 to 20 carbon atoms are And a group according to a combination thereof, or a group according to a combination of these and a linking group Lh.
  • aCy, hCy an aromatic ring
  • alkane structure preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms
  • a group having 2 to 40 carbon atoms preferably 2 to 30 carbon atoms, more preferably 2
  • the group having an alkane structure, the group having an alkene structure, or the group having an alkyne structure may be linear or cyclic, and may be linear or branched.
  • this trivalent or higher valent linking group is referred to as a linking group Lm.
  • two or more substituents R P1 may be substituted on the same structural unit.
  • those in which two or more R P1 are substituted on the benzene ring are also exemplified as preferred embodiments of the present invention.
  • the polymer main chain and the substituent R P1 in the formulas (1) to (6) may have a substituent T as long as the effects of the present invention are exhibited.
  • the specific polymer is preferably a copolymer.
  • the copolymer component preferably contains at least one of structural units represented by any of the following formulas (1-1) to (1-6) (hereinafter sometimes referred to as other structural units).
  • each of the substituents R P2 is independently a substituent containing a polymerizable group
  • R P4 is a hydrogen atom or a methyl group.
  • the polymerizable group contained in R P2 is preferably the above Ps.
  • RP2 may have a linking group between the polymerizable group and the main chain, and in the case of a divalent linking group, examples of the linking group L are mentioned. An example of Lm is given.
  • R P2 When there are two or more R P2 in the formulas (1-1) to (1-6), that is, (R P2 ) n (n is a natural number of 1 or more), a plurality of R P2 are bonded to each other. A ring may be formed. Also, R P2 may form a ring attached to the backbone. Further, the formula (1-1) backbone and substituent T to the extent that the effect of the present invention is the substituent R P2 of to Formula (1-6) may be substituted.
  • RP2 is preferably the following formula (T2).
  • the formula weight of RP2 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
  • L 4 is the above-described linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable.
  • n6 is an integer of 0-6.
  • P is a polymerizable group Ps.
  • n7 is an integer of 1 to 6, preferably 1 or 2.
  • the terminal L 4 may be a tetravalent or higher linking group and all P may be substituted, but two or more L 4 may be substituted with P. Good.
  • the specific polymer includes a structural unit represented by the formula (1), the other structural unit is preferably a structural unit represented by the formula (1-1).
  • the formulas (2) to (6) preferably include structural units represented by the formulas (1-2) to (1-6), respectively.
  • the specific polymer further includes a structural unit having no polymerizable group (sometimes referred to as “further structural unit”).
  • the other structural unit preferably has a skeleton of the formulas (1-1) to (1-6) defined in the other structural unit.
  • the substituent R P2 becomes a substituent R P3 having no polymerizable group.
  • two or more of R P2 in the other structural units (1-1), (1-2), (1-4), and (1-6) may be substituted with a ring structure group.
  • the substituent T may be substituted on the other structural unit within the range in which the effect of the present invention is exerted on the main chain portion and R P3 .
  • RP3 is preferably the following formula (T3).
  • the formula weight of RP3 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
  • L 5 is the above linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable.
  • T 1 is the above-described substituent T, and examples thereof include an alkyl group, an aryl group, an alkoxy group, and an acyl group.
  • n9 is an integer of 1 to 6, preferably 1 or 2.
  • the terminal L 5 may be a tetravalent or higher linking group and all T 1 may be substituted, but two or more L 5 may be substituted with T 1. Good.
  • L 4 , L 5 , P and T 1 may have the substituent T as long as the effects of the present invention are exhibited.
  • an alkane structure group, an alkene structure group, an aryl structure group, or the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the structural unit represented by any one of the formulas (1) to (6) may constitute all of the polymer (homopolymer having a structural ratio of 100 mol%), Furthermore, it may be a copolymer with other structural units.
  • a structural unit having a group capable of leaving a leaving component for example, a structural unit represented by formula (1) to formula (6)) / other structural unit (a structural unit having a polymerizable group) ) /
  • the composition ratio of other structural units is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and more preferably 50 to 100 / 0 to 50/0 to 10 is more preferable, and may be 50 to 90/10 to 50/0 to 10.
  • the specific polymer may contain only one kind of each of a structural unit having a group capable of leaving a leaving component, another structural unit (a structural unit having a polymerizable group), and another structural unit. And 2 or more types may be included.
  • the total is preferably the above ratio.
  • the constitutional unit is substantially free of other constitutional units other than the constitutional unit having a group capable of leaving the leaving component and the constitutional unit having a polymerizable group. “Substantially not contained” means, for example, 5% by mass or less of all structural units, preferably 3% by mass or less, and more preferably 1% by mass or less.
  • the weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, further preferably 7,000 or more, and even more preferably 10,000 or more.
  • As an upper limit 2,000,000 or less is preferable, 1,500,000 or less is more preferable, and 1,000,000 or less is more preferable.
  • the measuring method of a weight average molecular weight shall be based on the method shown in the following Example.
  • the content of the specific polymer in the composition for forming a lower layer film for imprinting is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. It is more preferable that it is 1.5 mass% or more. As an upper limit, it is preferable that it is 10 mass% or less, It is more preferable that it is 7 mass% or less, It is further more preferable that it is 5 mass% or less, It is still more preferable that it is 4 mass% or less, 3 mass % Or less is even more preferable. By making this quantity more than the said lower limit, the effect by having mix
  • the content of the specific polymer with respect to the non-volatile component (meaning the solid content excluding the solvent in the composition) in the underlayer film-forming composition for imprints is preferably 90% by mass or more, It is more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • the upper limit is 100% by mass.
  • the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
  • One kind of specific polymer may be used, or two or more kinds thereof may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the substituent R P1 which forms a leaving component can be introduced into the main chain by a conventional method.
  • a desorption reaction accelerator is a compound that, when coexisting with a specific polymer in the system, acts on a specific polymer by a predetermined trigger and promotes a reaction for desorbing a desorbing component from the specific polymer.
  • the elimination reaction accelerator is a compound having an acidic functional group or a basic functional group.
  • the elimination reaction accelerator is preferably present as a precursor in the composition. Examples of the precursor include a compound that reacts by applying external energy such as heat and light, and is converted into an elimination reaction accelerator compound. Specific examples include thermal acid generators, photoacid generators, thermal base generators, photobase generators, thermal acid generators and photoacid generators are preferred, and thermal acid generators are more preferred.
  • the pKa of the elimination accelerator is preferably 2 or less, more preferably 1 or less, and even more preferably 0 or less.
  • the lower limit is not particularly defined, but may be, for example, ⁇ 10 or more.
  • the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, and still more preferably 8 or more.
  • the upper limit value is not particularly defined, but may be 15 or less, for example.
  • specific examples of the elimination reaction accelerator or its precursor include acid proliferators described in paragraphs 0012, 0017, and 0026 to 0037 of JP 2014-047329 A, and light described in paragraphs 0038 to 0040.
  • Acid generator thermal acid generator described in paragraph 0041, photobase proliferating agent described in paragraphs 0029 to 0066 of JP2012-237776, photobase generator described in paragraphs 0073 to 0087, paragraphs 0087 to 0090
  • a thermal base generator described in paragraphs 0012 to 0015 and 0023 to 0029 of Japanese Patent No. 5687442; a photoacid generator described in paragraphs 0033 to 0075 of WO 2009/123122;
  • the base generators described in paragraphs 0038 to 0069 of Kai 2011-236416 can be used, and among these, Of which are incorporated herein.
  • the content of the elimination reaction accelerator or its precursor is preferably 0.1% by mass or more of the nonvolatile component, more preferably 1.0% by mass or more, and 2.0% by mass or more. More preferably it is. As an upper limit, it is practical that it is 10.0 mass% or less, and may be 5.0 mass% or less. Only one type of elimination reaction accelerator or its precursor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the undercoat film-forming composition for imprinting may contain an alkylene glycol compound.
  • the alkylene glycol compound preferably has 3 to 1000 alkylene glycol structural units, more preferably 4 to 500, still more preferably 5 to 100, and more preferably 5 to It is more preferable to have 50 pieces.
  • the weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10,000, more preferably 200 to 5,000, still more preferably 300 to 3,000, and even more preferably 300 to 1,000.
  • the alkylene glycol compounds are polyethylene glycol, polypropylene glycol, mono- or dimethyl ether, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, monooleate, monoadipate, monosuccinate.
  • the acid ester include polyethylene glycol and polypropylene glycol.
  • the surface tension of the alkylene glycol compound at 23 ° C. is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more.
  • the upper limit of the surface tension is not particularly defined, but is, for example, 48.0 mN / m or less.
  • the alkylene glycol compound When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. Further preferred.
  • One type of alkylene glycol compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • a polymerization initiator may be included.
  • the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferred from the viewpoint of improving the crosslinking reactivity with the curable composition for imprints.
  • a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.
  • a plurality of photopolymerization initiators may be used in combination.
  • halogenated hydrocarbon derivatives eg, compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, compounds containing a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • oxime compounds are preferred. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.
  • acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • Commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
  • the content of the photopolymerization initiator used in the above-described imprint lower layer film-forming composition is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass in the nonvolatile component. %, More preferably 0.2 to 7% by mass.
  • the total amount becomes the said range.
  • a polymerization inhibitor may be included.
  • the polymerization inhibitor (B) according to the present embodiment is a compound having the ability to trap radicals generated in the curable main agent (A) before they undergo a growth reaction. Thereby, a polymerization inhibitor (B) acts so that superposition
  • the polymerization inhibitor (B) can be any of hydroquinones, catechols, phenothiazines, and phenoxazines.
  • Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, 2,6-di-tert- Mention may be made of phenolic compounds such as butyl-p-cresol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, hydroquinone and tert-butylhydroquinone.
  • polymerization inhibitor (B) examples include quinone compounds such as naphthoquinone and benzoquinone.
  • Specific examples of the polymerization inhibitor (B) include amine compounds such as phenothiazine, phenoxazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine.
  • Specific examples of the polymerization inhibitor (B) include N, such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
  • -Oxyl compounds can also be mentioned. The compounds listed here are merely examples, and the polymerization inhibitor (B) may be other compounds.
  • the content of the polymerization inhibitor is preferably 0.0001% by mass or more and 10.0% by mass or less of the solid component, more preferably 0.001% by mass or more and 1.0% by mass or less. More preferably, it is 005 mass% or more and 0.1 mass% or less. Only one type of polymerization inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that those total amounts become the said range.
  • non-volatile component mix blended with the underlayer film forming composition for imprints
  • thermal polymerization initiator and the like each component described in JP2013-036027A, JP2014-090133A, JP2013-189537A can be used.
  • the description in the above publication can be referred to.
  • it can also be set as the structure which does not contain surfactant substantially in the underlayer film forming composition for imprints. “Substantially not contained” means 0.1% by mass or less of the nonvolatile component in the composition for forming a lower layer film for imprinting.
  • the underlayer film forming composition for imprints contains a solvent.
  • the solvent preferably contains, for example, a compound having a boiling point of 250 ° C. or lower (solvent for the lower layer film) at a rate of 70.0% by mass or more at 23 ° C.
  • the nonvolatile component finally forms the lower layer film.
  • the lower film forming composition for imprinting preferably contains 80.0% by mass or more of the solvent for the lower layer film, more preferably 90.0% by mass or more, and more preferably 93.0% by mass or more. Preferably, it is 94.0 mass% or more, and 95.0 mass% or more, 98.0 mass% or more, and 99.0 mass% or more may be sufficient.
  • the solvent only 1 type may be contained in the underlayer film forming composition for imprint, and 2 or more types may be contained. When 2 or more types are included, the total amount is preferably within the above range.
  • the boiling point of the solvent for the lower layer film is preferably 230 ° C. or less, more preferably 200 ° C. or less, further preferably 180 ° C. or less, further preferably 160 ° C. or less, and 130 ° C. or less. Is more preferable.
  • the lower limit is 23 ° C., but practically 60 ° C. or higher.
  • the solvent for the lower layer film is preferably an organic solvent.
  • the solvent is preferably a solvent containing any one or more of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among these, it is preferable to use an aprotic polar solvent.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected.
  • alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (eg 1-methoxy-2-propanol), ethoxypropanol (eg 1-ethoxy-2-propanol), propoxypropanol (eg 1-propoxy-2- Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol).
  • methoxypropanol eg 1-methoxy-2-propanol
  • ethoxypropanol eg 1-ethoxy-2-propanol
  • propoxypropanol eg 1-propoxy-2- Propanol
  • methoxybutanol eg 1-methoxy-2-butanol, 1-
  • the propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate. It is particularly preferred.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
  • lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
  • acetate methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl amyl ketone are preferred.
  • cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone is preferable.
  • alkylene carbonate propylene carbonate is preferable.
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
  • ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
  • a solvent having a flash point (hereinafter also referred to as fp) of 30 ° C. or higher.
  • fp a solvent having a flash point
  • examples of such components include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C.), Cyclohexanone (fp: 30 ° C.), pentyl acetate (fp: 45 ° C.), methyl 2-hydroxyisobutyrate (fp: 45 ° C.), ⁇ -butyrolactone (fp: 101 ° C.) or propylene carbonate (fp: 132 ° C.) is preferred.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
  • solvents for the lower layer film water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate At least one is more preferable.
  • a conventionally known storage container can be used as the storage container for the composition for forming an underlayer film for imprint.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the curable composition for imprints preferably contains a polymerizable compound, and preferably contains a polymerizable compound having an aromatic ring.
  • the polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Moreover, it is preferable that both a monofunctional polymerizable compound and a polyfunctional polymerizable compound are included.
  • the molecular weight of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.
  • the molecular weight is preferably 1,000 or less, more preferably 800 or less, further preferably 300 or less, and even more preferably 270 or less. There exists a tendency which can suppress volatility by making molecular weight more than the said lower limit. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
  • the boiling point of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 85 ° C. or higher, more preferably 110 ° C.
  • the boiling point is not particularly defined, but for example, the boiling point can be 350 ° C. or lower.
  • the type of polymerizable group possessed by the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, and examples thereof include ethylenically unsaturated groups and epoxy groups, with ethylenically unsaturated groups being preferred.
  • ethylenically unsaturated group a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.
  • the type of atoms constituting the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but should be composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. Is preferable, and it is more preferably composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.
  • a preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a linear or branched hydrocarbon chain having 4 or more carbon atoms.
  • the hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, preferably an alkyl chain or alkenyl chain, and more preferably an alkyl chain.
  • the alkyl chain represents an alkyl group and an alkylene group.
  • an alkenyl chain represents an alkenyl group and an alkenylene group
  • an alkynyl chain represents an alkynyl group and an alkynylene group.
  • a linear or branched alkyl group or an alkenyl group is more preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is more preferable.
  • the linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 10 or more carbon atoms, and more carbon atoms. 12 or more is more preferable.
  • the upper limit value of the carbon number is not particularly defined, but can be, for example, 25 or less.
  • the linear or branched hydrocarbon chain may contain an ether group (—O—), but preferably does not contain an ether group from the viewpoint of improving releasability.
  • a monofunctional polymerizable compound having a hydrocarbon chain By using such a monofunctional polymerizable compound having a hydrocarbon chain, the elastic modulus of the cured product (pattern) is reduced and the releasability is improved with a relatively small addition amount. Further, when a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured product (pattern) can be reduced, and the releasability can be further improved.
  • Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably one having 10 or more carbon atoms, further preferably 11 or more carbon atoms, and still more preferably 12 or more carbon atoms. Moreover, 20 or less carbon atoms are preferable, 18 or less carbon atoms are more preferable, 16 or less carbon atoms are more preferable, and 14 or less carbon atoms are still more preferable.
  • the branched alkyl group having 10 or more carbon atoms is preferably one having 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, still more preferably 10 to 14 carbon atoms, More preferably, the number of carbon atoms is 10 to 12.
  • a linear or branched alkyl group having 1 or more carbon atoms is more preferably a linear alkyl group. preferable.
  • the carbon number of the alkyl group is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the alicyclic ring, aromatic ring or aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
  • the number of rings is preferably 2 or 3.
  • the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • Specific examples of the ring include an example of the ring Cz described later.
  • the monofunctional polymerizable compound used in the curable composition for imprints is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are bonded directly or via a linking group.
  • a compound in which any one of the above groups (1) to (3) and a polymerizable group are directly bonded is more preferable.
  • Examples of the linking group include —O—, —C ( ⁇ O) —, —CH 2 —, or a combination thereof.
  • the monofunctional polymerizable compound used in the present invention includes (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. preferable.
  • the monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).
  • R 12 is an alkyl group (preferably having a carbon number of 1 to 36, preferably 1 to 30, more preferably 1 to 24), or an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms). 6 is more preferred), an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) and an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, it represents a group of at least one selected from 2-5, or a combination thereof.
  • R 11 represents a hydrogen atom or a methyl group.
  • L 11 represents a single bond or the linking group L, and is preferably an alkylene group or an alkenylene group.
  • R 12 and L 11 may combine with or without a linking group L to form a ring.
  • R 12 and L 11 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, may be bonded to R 12 , or may be bonded to L 11 to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • the preferred range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring for R 12 is the same as ring Cz described later.
  • Examples of the monofunctional polymerizable compound of the first embodiment include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples.
  • the first group is more preferable than the second group.
  • a preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a cyclic structure.
  • the cyclic structure is preferably a 3- to 8-membered monocyclic ring or condensed ring.
  • the number of rings constituting the fused ring is preferably 2 or 3.
  • the cyclic structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • a single ring is more preferable.
  • the number of cyclic structures in one molecule of the polymerizable compound may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a condensed ring, the condensed ring is considered as one cyclic structure.
  • Examples of the monofunctional polymerizable compound according to the second embodiment include the following compounds. However, it goes without saying that the present invention is not limited to these examples. Of the compounds described in the first embodiment, compounds having a cyclic structure are also exemplified as preferred compounds of this embodiment.
  • a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as it does not depart from the spirit of the present invention, and monofunctional polymerizable compounds described in JP-A-2014-170949 can be used. Examples of the polymerizable compound are included in the present specification.
  • the content of the monofunctional polymerizable compound used in the curable composition for imprints with respect to the total polymerizable compound is preferably 6% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. 12 mass% or more is more preferable.
  • the content is more preferably 60% by mass or less, and may be 55% by mass or less.
  • only one monofunctional polymerizable compound may be contained, or two or more kinds may be contained. When 2 or more types are included, the total amount is preferably within the above range.
  • the polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but preferably contains at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring. More preferably, it contains at least one heterocyclic ring.
  • a compound containing at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring may be referred to as a ring-containing polyfunctional polymerizable compound.
  • the molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, and further preferably 350 or less. .
  • the upper limit of the molecular weight is not particularly defined, but can be, for example, 200 or more.
  • the number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is 2 or more, preferably 2 to 7, more preferably 2 to 4, more preferably 2 or 3. 2 is more preferable.
  • the type of polymerizable group possessed by the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but examples thereof include ethylenically unsaturated groups and epoxy groups. preferable.
  • ethylenically unsaturated group a (meth) acryloyl group is more preferable, and an acryloyl group is more preferable.
  • Two or more polymerizable groups may be contained in one molecule, or two or more polymerizable groups of the same type may be contained.
  • the type of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but is composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is preferable that it is composed only of atoms selected from a carbon atom, an oxygen atom and a hydrogen atom.
  • the ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be monocyclic or condensed, but is preferably monocyclic.
  • the number of rings is preferably 2 or 3.
  • the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocyclic ring, but is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring.
  • Specific examples of the ring include an example of the ring Cz.
  • the number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be one or two or more, but preferably one or two, more preferably one. . In the case of a condensed ring, one condensed ring is considered.
  • the structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Or a divalent linking group)-(polymerizable group).
  • the linking group is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms.
  • the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably represented by the following formula (I-2).
  • Q is an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms) or an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 10 represents a 1 + q-valent group having at least one selected from 10 and more preferably an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 5 carbon atoms).
  • R 21 and R 22 each independently represents a hydrogen atom or a methyl group.
  • L 21 and L 22 each independently represent a single bond or the above linking group L.
  • Q and L 21 or L 22 may combine with or without a linking group L to form a ring.
  • Q, L 21 and L 22 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, may be bonded to Q, or may be bonded to L 21 or L 22 to form a ring.
  • When there are a plurality of substituents T they may be the same or different.
  • the preferable range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in Q includes ring Cz described later.
  • q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • Q has a structure in which a plurality of alicyclic rings, a plurality of aromatic rings, a plurality of aromatic heterocyclic rings, an alicyclic ring and an aromatic ring, an alicyclic ring and an aromatic heterocyclic ring, and an aromatic ring and an aromatic heterocyclic ring are connected. You may do it.
  • Examples of the structure in which the aromatic rings are linked include the structures of the above formulas Ar1 to Ar5.
  • Examples of the polyfunctional polymerizable compound used in the curable composition for imprints include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples.
  • the first group is more preferable.
  • the curable composition for imprints may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
  • a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
  • compounds represented by the following formula (I-3) are preferable.
  • L 30 is a group having a linear or branched alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3), or a group having a linear or branched alkene structure (having 2 carbon atoms).
  • To 12 are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable.
  • a linear or branched alkyne structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3).
  • R 25 and R 26 each independently represents a hydrogen atom or a methyl group.
  • L 25 and L 26 each independently represent a single bond or the above linking group L.
  • L 30 and L 25 or L 26 may combine with or without a linking group L to form a ring.
  • L 25 , L 26 and L 30 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • a hetero linking group (O, S, NR N ) may be interposed in L 30 .
  • the number of intervening hetero linking group is preferably a rate of one having 1 to 6 carbon atoms, L 30.
  • Examples of other polyfunctional polymerizable compounds used in the curable composition for imprints include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A No. 2014-170949. Is included herein. More specifically, for example, the following compounds are exemplified.
  • the ring Cz examples include the following aromatic rings, aromatic heterocyclic rings and alicyclic rings.
  • the aromatic ring contained in the compound containing an aromatic ring is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10.
  • Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring.
  • the aromatic ring may have a structure in which a plurality of aromatic rings are connected, and examples thereof include a biphenyl ring and a bisphenyl ring.
  • the aromatic heterocyclic ring preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 5.
  • thiophene ring examples include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole.
  • the alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 and even more preferably 6 to 10.
  • cyclopropane ring examples include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, Examples include a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.
  • the polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total polymerizable compound in the curable composition for imprints. 55 mass% or more is still more preferable, 60 mass% or more may be sufficient, and 70 mass% or more may be sufficient. Moreover, it is preferable that an upper limit is less than 95 mass%, it is further more preferable that it is 90 mass% or less, and it can also be 85 mass% or less.
  • the curable composition for imprints may contain only one type of polyfunctional polymerizable compound or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • 85% by mass or more of the composition is preferably a polymerizable compound, more preferably 90% by mass or more is a polymerizable compound, and 93% by mass or more. More preferably, it is a polymerizable compound.
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
  • the polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
  • the dispersion term component, polar term component, and hydrogen bond term component of the HSP vector of the curable composition for imprints are set by the methods described in the examples described later.
  • the curable composition for imprints may contain additives other than the polymerizable compound.
  • additives include a polymerization initiator, a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor and the like.
  • Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP2013-036027A, JP2014-090133A, and JP2013-189537A. The contents of which are incorporated herein. The description of the above publication can be referred to for the preparation of the curable composition for imprints and the method for forming the film (pattern forming layer), and the contents thereof are incorporated in the present specification.
  • the viscosity of the curable composition for imprints is preferably 20.0 mPa ⁇ s or less, more preferably 15.0 mPa ⁇ s or less, and may be 11.0 mPa ⁇ s or less, It may be 9.0 mPa ⁇ s or less. Although it does not specifically limit as a lower limit of the said viscosity, For example, it can be 4.0 mPa * s or more, Furthermore, it can be 5.0 mPa * s or more.
  • the surface tension ( ⁇ Resist) of the curable composition for imprints is preferably 29.0 mN / m or more, more preferably 30.0 mN / m or more, and further preferably 31.0 mN / m or more. preferable.
  • the upper limit of the surface tension is not particularly limited, but it is preferably 42.0 mN / m or less from the viewpoint of imparting the relationship with the lower layer film and inkjet suitability. More preferably, it may be 38.0 mN / m or less.
  • the Onishi parameter of the curable composition for imprints is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.7 or less.
  • the lower limit value of the Onishi parameter of the curable composition for imprints is not particularly defined, but may be, for example, 1.0 or more, or 2.0 or more.
  • the Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formulas for the polymerizable compound of the curable composition for imprints.
  • Onishi parameter sum of the number of carbon, hydrogen and oxygen atoms / (number of carbon atoms-number of oxygen atoms)
  • the Hansen Solubility Parameter (HSP) vector of the polymerizable compound contained in the curable composition for imprints (I)
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
  • the polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
  • the dispersion term component, polar term component, and hydrogen bond term component of the HSP vector are each set by the method described in the examples described later.
  • the content of the solvent in the curable composition for imprints is preferably 5% by mass or less of the curable composition for imprints, more preferably 3% by mass or less, and 1% by mass. More preferably, it is as follows.
  • the curable composition for imprints is a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, and still more preferably a weight average molecular weight of 10,000 or more. ) May not be substantially contained. “Containing substantially no polymer” means, for example, that the polymer content is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not contained at all. Is more preferable.
  • the container for the curable composition for imprints used in the present invention a conventionally known container can be used.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the present invention discloses a kit comprising a composition for forming an underlayer film for imprinting and a curable composition for imprinting containing a polymerizable compound.
  • the kit of the present invention comprises a Hansen solubility parameter of a desorbing component (a compound represented by formula (r1) or (r2) or a compound represented by formula (r1-1)) and Hansen of a curable composition for imprints.
  • the ⁇ HSP value calculated by the following mathematical formula (H1) based on the solubility parameter is preferably 5 or less, more preferably 7.0 or less, further preferably 5.0 or less, and 4.0. More preferably, it is as follows. The lower limit may be 0, but is practically 0.1 or more.
  • ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1)
  • ⁇ D is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the elimination component.
  • ⁇ P is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hansen solubility parameter vector of the elimination component.
  • ⁇ H is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the imprint curable composition and the hydrogen bond term component of the Hansen solubility parameter vector of the desorption component.
  • a preferred embodiment of the kit of the present invention includes a laminate formed from the kit.
  • the laminate of the present embodiment comprises an underlayer film formed from the above-described imprint underlayer film-forming composition, and an imprint layer formed from the above-mentioned curable composition for imprints and located on the surface of the underlayer film. It is preferable to have.
  • the manufacturing method is not particularly limited, a manufacturing method including applying the curable composition for imprints to the surface of the lower layer film formed from the lower layer film forming composition for imprints using the kit described above. Can be mentioned.
  • the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method (IJ method).
  • the method for producing a laminate includes a step of applying the above-described imprint lower layer film-forming composition in a layer form on a substrate. Preferably includes heating (baking) at 150 to 250 ° C. (process temperature).
  • a method for producing a cured product pattern according to a preferred embodiment of the present invention is a method for producing a cured product pattern using the above-described kit, wherein a lower layer film-forming composition for imprinting is applied to a lower layer on a substrate.
  • An underlayer film forming step of forming a film An application step of applying the curable composition for imprints to the surface of the underlayer film, the curable composition for imprints, and a pattern for transferring the pattern shape
  • a method for forming a cured product pattern (a method for producing a cured product pattern) will be described with reference to FIG. It goes without saying that the configuration of the present invention is not limited by the drawings.
  • Lower layer formation process the lower layer film 2 is formed on the substrate 1 as shown in FIGS. 1 (1) and (2).
  • the lower layer film is preferably formed by applying the lower film forming composition for imprinting in a layer form on the substrate.
  • the application method of the composition for forming an underlayer film for imprinting on the substrate is not particularly defined, and generally known application methods can be employed. Specifically, as an application method, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scanning method, or ink jet method And a spin coating method is preferable. Moreover, after applying the lower film
  • the thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, and may be 5 nm or more, or 7 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, may be 15 nm or less, and further 10 nm or less. Also good.
  • the expandability (wetting property) on the lower layer film of the curable composition for imprinting is improved, and a uniform residual film after imprinting can be formed.
  • the remaining film after imprinting becomes thin, film thickness unevenness hardly occurs, and the remaining film uniformity tends to be improved.
  • a silicon substrate is not particularly defined, and the description in paragraph 0103 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0183127) can be referred to. Is incorporated herein by reference.
  • the curable composition 3 for imprinting is applied to the surface of the lower layer film 2.
  • the method for applying the curable composition for imprints is not particularly defined, and paragraph 0102 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0199592). The contents of which are incorporated herein by reference.
  • the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method. Moreover, you may apply
  • the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to dispose the droplets on the surface of the lower layer film with an interval between the droplets.
  • the interval between the droplets is preferably 10 to 1000 ⁇ m.
  • the liquid drop interval is the arrangement interval of the ink jet nozzles.
  • the volume ratio of the lower film 2 and the film-like curable composition for imprint 3 applied on the lower film is preferably 1: 1 to 500, more preferably 1:10 to 300. A ratio of 1:50 to 200 is more preferable.
  • the manufacturing method of the laminated body which concerns on preferable embodiment of this invention is a method of manufacturing using the kit of this invention, Comprising: On the surface of the lower layer film formed from the said lower layer film formation composition for imprints, Applying a curable composition for imprints.
  • the manufacturing method of the laminated body which concerns on preferable embodiment of this invention includes the process of applying the said underlayer film formation composition for imprints on a board
  • Mold contact process For example, as shown in FIG. 1 (4), the curable composition for imprints 3 is brought into contact with the mold 4 having a pattern for transferring the pattern shape. Through such a process, a desired cured product pattern (imprint pattern) is obtained. Specifically, in order to transfer a desired pattern to the film-shaped curable composition for imprints, the mold 4 is pressed against the surface of the film-shaped curable composition for imprints 3.
  • the mold may be a light transmissive mold or a light non-transmissive mold.
  • a light-transmitting mold it is preferable to irradiate the curable composition 3 for imprinting with light from the mold side.
  • a light-impermeable mold it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side.
  • a light transmissive mold and irradiate light from the mold side is more preferable to use.
  • the mold that can be used in the present invention is a mold having a pattern to be transferred.
  • the mold pattern manufacturing method in particular is not restrict
  • cured material pattern manufacturing method which concerns on preferable embodiment of this invention can also be used as a mold.
  • the material constituting the light-transmitting mold used in the present invention is not particularly limited, but includes a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), and polycarbonate resin, a transparent metal vapor-deposited film, and polydimethylsiloxane. Examples thereof include a flexible film, a photocured film, and a metal film, and quartz is preferable.
  • the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited as long as it has a predetermined strength.
  • Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions.
  • the mold pressure is preferably selected from a range in which the residual film of the curable composition for imprint hitting the mold convexity is reduced while ensuring the uniformity of mold transfer.
  • the curable composition for imprints is irradiated with light to form a cured product.
  • the irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount necessary for curing.
  • the amount of irradiation necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints.
  • an ultraviolet light is illustrated.
  • the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
  • a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light.
  • a preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁇ 1 Pa to normal pressure.
  • the exposure illuminance is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 .
  • the exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second.
  • Exposure amount is preferably in a range of 5 ⁇ 1000mJ / cm 2, and more preferably in the range of 10 ⁇ 500mJ / cm 2.
  • the film-shaped curable composition for imprints is cured by light irradiation, and then is further cured by applying heat to the cured pattern as necessary. A process may be included.
  • the temperature for heat-curing the curable composition for imprints after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
  • the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • the cured product and the mold are separated (FIG. 1 (5)).
  • the obtained cured product pattern can be used for various applications as described later. That is, in this invention, the laminated body which has further the hardened
  • the cured product pattern formed by the method for producing a cured product pattern is used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element.
  • the present invention discloses a circuit board manufacturing method including a step of obtaining a cured product pattern by a cured product pattern manufacturing method according to a preferred embodiment of the present invention.
  • the step of performing etching or ion implantation on the substrate using the cured product pattern obtained by the method for manufacturing a cured product pattern as a mask, and the formation of the electronic member are formed. You may have a process.
  • the circuit board is preferably a semiconductor element.
  • the present invention discloses a method for manufacturing an electronic device, which includes a step of obtaining a circuit board by the method for manufacturing a circuit board, and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
  • a grid pattern is formed on the glass substrate of the liquid crystal display device using the pattern formed by the above-described cured product pattern manufacturing method, and polarized light having a large screen size (for example, 55 inches or more than 60 inches) with little reflection and absorption. It is possible to manufacture the plate at a low cost. For example, a polarizing plate described in JP-A-2015-132825 and International Publication No. 2011-132649 can be produced. One inch is 25.4 mm.
  • the cured product pattern formed in the present invention is also useful as an etching resist (lithographic mask) as shown in FIGS.
  • the cured product pattern As an etching resist, first, for example, a silicon substrate (such as a silicon wafer) on which a thin film such as SiO 2 is formed as a substrate, and the cured product pattern manufacturing method on the substrate, for example, A fine cured material pattern of nano or micron order is formed.
  • a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed.
  • the lower limit of the size of the cured product pattern formed by the cured product pattern manufacturing method is not particularly defined, but can be, for example, 1 nm or more.
  • a method for producing an imprint mold comprising: a step of obtaining a cured product pattern by a method of producing a cured product pattern on a substrate; and a step of etching the substrate using the obtained cured product pattern.
  • a desired cured product pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • the cured product pattern has particularly good etching resistance against dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a lithography mask.
  • FIG. 2 is a plan view schematically showing a wet spread state of the curable composition for imprints when the curable composition for imprints is applied to the surface of the lower layer film by an inkjet method.
  • IJ inkjet
  • droplets of the curable composition for imprints 22 are dropped on the surface of the lower layer film 21 at equal intervals.
  • FIG. 2A When the mold is brought into contact therewith, the droplets spread on the lower layer film 21 and become film-shaped curable compositions for imprints 22a, 22b, 22c (FIGS. 2B, 2C, 2C). (D)).
  • the state of the curable composition for imprints 22b is completely on the lower layer film 21.
  • a film that does not spread is formed. That is, a region 23 having a thin film thickness or no film may be generated. If it becomes like this, the part in which the curable composition for imprints is not fully filled will arise in the pattern of a mold, and the part without a pattern will be made in an imprint layer. For example, when etching is performed using a pattern of an imprint layer having a defect or an insufficiently thick portion in such a part as a mask, a thin region or a region 23 without a film and another region 22b.
  • the lower layer film forming composition for imprints of the present invention the interfacial tension between the lower layer film formed thereby and the curable composition for imprints is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state of FIG. As a result, the curable composition for imprints can be filled in the mold accurately and sufficiently, and good patterning with uniform thickness can be achieved in the formed imprint layer. In addition, the improvement of filling property enables high-speed imprinting, which can lead to an improvement in throughput.
  • the pattern formed in the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state image sensor, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), a liquid crystal display.
  • a recording medium such as a magnetic disk
  • a light receiving element such as a solid-state image sensor
  • a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
  • a liquid crystal display such as a magnetic disk
  • a light receiving element such as a solid-state image sensor
  • a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
  • a liquid crystal display such as a liquid crystal display.
  • Optical devices such as devices (LCD), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropattern formation using self-assembly of block copolymers (directed self-assembly, DSA) It can be preferably used in the preparation of the guide pattern, etc. for.
  • LCD liquid crystals
  • DSA directed self-assembly
  • Tetrahydrofuran (THF) (300 g) and G-1A (10 g) are added to a three-necked flask with N 2 flow, cooled to 0 ° C., and LiAlH 4 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 3 g) is gradually added. In addition, aging was performed for 2 hours. Thereafter, water (3 g), a 15% aqueous sodium hydroxide solution (3 g) and water (9 g) were added and aged for 1 hour. Then, the target compound (intermediate G-1B) was synthesized by filtering and concentrating the filtrate.
  • G-1D (10 g) and cyclohexane (100 g) were added to a three-necked flask with N 2 flow, cooled to 0 ° C., and a 20% butyl lithium cyclohexane solution (Tokyo Chemical Industry Co., Ltd., 12 mL) was added dropwise. Aged for time. Thereafter, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 3 g) was added dropwise and aging was performed for 1 hour. Thereafter, THF (100 g) and 1M HCl aqueous solution were added, and aging was performed for 5 hours.
  • PGMEA (30 g) was added to a three-necked flask with N 2 flow and heated to 60 ° C.
  • 2-Hydroxyethyl Methacrylate (Tokyo Chemical Industry Co., Ltd., 13 g, 100 mmol)
  • G-1E 26 g, 100.0 mmol
  • photo radical polymerization initiator (Fuji Film Wako Pure Chemical Industries, Ltd., V-65, 1) 0.0 g, 4.0 mmol) was dissolved in PGMEA (70 g), and the resulting mixture was added dropwise over 2 hours at a temperature where the internal temperature of the flask did not exceed 65 ° C., followed by aging at 90 ° C. for 4 hours. It was.
  • PGMEA 45.38 g
  • intermediate G-1F (19.7 g, 100.0 mmol)
  • triethylamine manufactured by Tokyo Chemical Industry Co., Ltd., 15 g, 150.0 mmol
  • PGMEA 45.38 g
  • Acryloy Chylide 14 g, 150.0 mmol
  • composition for forming lower layer film Each component is blended as shown in Tables 1 to 4 below, and two-stage filtration is performed with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a UPE filter (ultra high molecular weight polyethylene) having a pore size of 0.003 ⁇ m.
  • PTFE polytetrafluoroethylene
  • UPE ultra high molecular weight polyethylene
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 80 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film
  • the obtained lower layer film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed using LC / MS.
  • THF tetrahydrofuran
  • curable composition for imprint Each compound shown in Table 5 was mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry) as a polymerization inhibitor was further polymerized among the compounds shown in the table.
  • the curable composition for imprints was obtained by adding 200 mass ppm (0.02 mass%) to the total amount of the functional compound. This was two-stage filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.003 ⁇ m.
  • PTFE polytetrafluoroethylene
  • ⁇ Surface tension> The surface tension was measured at 23 ° C. using a surface tension meter SURFACETENSOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is indicated by mN / m. Two samples were prepared for each level, measured three times each, and a total of six arithmetic average values were adopted as evaluation values.
  • ⁇ HSP Hansen solubility parameter
  • ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1)
  • the Hansen solubility parameter when there are a plurality of compounds in each calculation target component (for example, when there are two or more desorption components), the value of the most abundant component (mass basis) among the corresponding compounds is adopted. In addition, when there are two or more kinds of the most abundant components, the average value is determined according to the mixing ratio.
  • Tables 1 to 4 show the distance ( ⁇ HSP) of the Hansen solubility parameter between the desorbing component and the curable composition calculated by the formula (H1).
  • the weight average molecular weight (Mw) of the polymer was defined as a polystyrene equivalent value according to gel permeation chromatography (GPC measurement).
  • the apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) were used as columns.
  • THF tetrahydrofuran
  • a UV ray (ultraviolet) wavelength 254 nm detector was used.
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 150 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film
  • the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc.
  • a quartz mold (rectangular line / space pattern (1/1), line width 40 nm, groove depth 100 nm, line edge roughness 3.5 nm) is placed thereon so as to be in contact with the curable composition layer for imprinting, and a quartz wafer From the side, exposure was performed at 300 mJ / cm 2 using a high-pressure mercury lamp. After the exposure, the quartz wafer was separated and the peeling force at that time was measured. This peeling force corresponds to the adhesion force F (unit: N).
  • the peeling force was measured according to the method for measuring the peeling force described in Comparative Examples described in paragraph numbers 0102 to 0107 of JP 2011-209777 A. That is, it was performed according to the peeling steps 1 to 6 and 16 to 18 in FIG. A: F ⁇ 45N B: 45N> F ⁇ 30N C: 30N> F ⁇ 20N D: 20N> F
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Thereafter, heating was performed using a hot plate at 150 ° C. for 3 minutes under baking conditions in an air atmosphere to form a lower layer film on the adhesion layer. The thickness of the obtained lower layer film was about 10 nm.
  • the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc.
  • T-1, T-4, T-5, T-6 and T-7 are photoacid generators.
  • T-2 is a thermal base generator.
  • T-3 is a thermal acid generator.
  • the underlayer film forming composition for imprints of the present invention contains a polymer that desorbs a specific desorbing component, and when used in combination with the curable composition for imprints. It was found that excellent wettability and good adhesion were exhibited (Examples 1 to 21). On the other hand, it was found that if the desorbing component does not desorb, or even if the desorbing component desorbs, it does not take a specific chemical structure and is inferior in wettability or wettability (Comparative Examples 1 to 3).
  • a quartz mold having a pattern with a width of 500 nm was brought into contact with the film of the curable composition for imprints produced in each example. Thereafter, the film was cured by irradiating ultraviolet rays from the mold side. Subsequently, the mold was pulled apart to obtain a cured product pattern to which the mold pattern was transferred. As a result, it was confirmed that a good pattern could be formed in any cured product.

Abstract

L'invention concerne une composition de formation de film de sous-couche pour impression qui contient un polymère et un solvant, et qui est telle qu'un composé spécifique de masse moléculaire supérieure ou égale à 210 est libéré dudit polymère lorsqu'elle est transformée en film et soumise à un étuvage à 80°C. Enfin, l'invention concerne une composition durcissable pour impression associée à cette composition de formation de film de sous-couche pour impression, et un kit mettant en œuvre celles-ci.
PCT/JP2019/008277 2018-03-07 2019-03-04 Composition de formation de film de sous-couche pour impression, composition durcissable pour impression, et kit WO2019172156A1 (fr)

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JP2020505001A JP7017623B2 (ja) 2018-03-07 2019-03-04 インプリント用下層膜形成組成物、インプリント用硬化性組成物、キット

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WO2021060339A1 (fr) * 2019-09-26 2021-04-01 富士フイルム株式会社 Composition de formation de film adhésif, film adhésif, stratifié, procédé de production pour stratifié, procédé de production pour motif et procédé de production pour élément à semi-conducteur
WO2021125036A1 (fr) * 2019-12-18 2021-06-24 日産化学株式会社 Composition pour former un film de réserve sous-jacent pour nano-impression

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